Aminoanthraquinone sulfonamides



Patented Nov. 2, 1948 AMINOANTHRAQUINONE SULFONAMIDES Curt G. Vogt, Union, N. J., assignor to General;

Aniline & Film Corporation, New York, N. Y., a

corporation of Delaware No Drawing. Application June 21, 1946, Serial No. 678,356

3 Claims.

Thiscinventionrelates ,to new-compounds, ,mcrev particularly to new aciddyestuffs of the aminoanthraquinone series whiclriir the free state may be represented thecgeneraliormulazx whereinX and Y each" represent a saturated aliphatic radical, such "as alkylf radicals; 'alicyclic radicals, such as" cyclo'l'iexyl and, deca'hydro naphthalene radicals, or aromatic'ra'dicals ofthe' benzene, naphthalene and hydrogenated naphthalene series, said radicals--inay, be substituted by carboxy, carbalkcxy; allioxy; acyloxy; hydroxy, halogen, sulfo and secondary and? tertiary alkylamino groups and Avrcpresents a bivalent alkylene radical which with the nitrogen atom on the sulionyl group constitutes a 5' to 7 membered heterocyclic ring.

The new compounds dye animal and nylon (super-polyamide) fibers fi'omlan acid bath clear blue to greenish-blue.shades-0f generally good fastness properties.

My new dyestufis maybe prepared by bringing together in am aqueous medium l-aminolbromoanthraquinoneazesulfonictacid sodium salt,

an aminobenzenesulfonarnide, a hydro-genion; acceptor, such as sodiumtcarbonate or' bicarbonate, and a catalyst, such as copper, cuprous or' cupric'salt s; e. g., cuprous chloride, and heating until condensation'is complete. The product dyestuii maybe" isolated" by" acidifying the reaction mixture or byth'e additionor a'salt'thereto such as'sodiumchlorider bymeans'ofwell known'procedures:

The amirmbenzenesulfonamides employed as 22 intermediates inlthe preparation of the new compoundsmay lee-prepared by reacting chlorobenzoic acid with chlorosulfonic acid to obtain the carbcxychlorobenzenesulfonylchloride, which, in turn, is reacted with-the selcted primary ow secondary amino compoundor alicycliedmine to produce the carboxychlorobenzenesulfonamideQ The latter is then aminated with ammonium hydroxide 'in the presence=of a; copper catalyst, e. glycoppersulfate, to"obtain"t'lie;desiredj amino= carboxybenzenesulfonamide: j j

Amongj'the amino-compounds "which may be:- employ'ed'ior the"preparation ofthe-intermediate" arninobenzenesulfonamides; are, for" exarnpley mono anddi methylamine; monoanddiethyl amine, mono andidi isopropyl:amine; cyclohexr ylamine, hex'ahydrobenzylamineyhexahydroanthranilic acid, N-methyl glycine, glycine, alanine, ethyl w aminocaproate, taurine, N methyl taurine, fi-aminoethy1 acetate, mono; and diethanolamine, B-ethoxyethylaminai fl-bromoethylamine, p-toluidine, 4-amino-ox ylene, 2.-"nitro-p anisidine, 0-, mor p-aminobenzoic acid, 5-aminosalicylic acid, 2-amino-4i methylbenzoic acid, 5-nitro-2-aminobenzoiv,acid, Z-chloro-paminobenzoic acid, aniline=;o, 'mor p-sulfonic acid, p-phenylenediamine, li-hydroxy-4-amino-2- naphthoic acid, 3-hyroxy-7-arninb-2-naphthoic acid, ac.-tetrahydro=a-naphthylamine, and a1.- tetrahydrom naphthylamine; etc. Among the alicyclic imines suitable for the preparation of the intermediates'may be mentioned, for example, tetramethylenemiminee (nyrnol idinel ',r..pentameth-L: ylenez; imine: (piperidine); 2e andaBI-methylfiple eridine; hexamethylene imine'; etc:

The invention is further illustrated:: thefollowing specific examples toiwhich, however, it is not intended that it be limited. Parts are by weightr 1 Example 1 (i) NH2 -COOH OOOH - SOzNH and dyes animal fibers from an acid bath attractive blue shades of good properties.

Example 2 Following essentially the procedure of Example 1, a mixture of 24.5 parts of 5-(3'-carboxy- 4'-hydroxyphenylsulfamy1) -anthranilic acid, 20.2

COOH

SOINHQOH It dyes wool from an acid bath attractive greenish-blue shades of good fastness, especially to light. When dyed by the monochrome method, the shade is much greener.

Example 3 To 20 parts of 5(N-(2-carboxyphenyl) -N'- methylsulfamyl) -anthranilic acid and 20.5 parts of sodium acetate in 150 parts of water at 80 C. was added a suspension of 12.1 parts of lamino-4-bromoanthraquinone-2-sulfonic acid sodium salt in 300 parts of water, also at 80 C. 1 part of cuprous chloride was added and the reaction mixture heated to 95 C. and held at this temperature under stirring for three and onehalf' hours. The reaction mixture was cooled to 75 C. and 110 parts of sodium chloride solution aqueous) were added slowly. This mixture was allowed to cool to 40 C. and filtered.

The dyestufi was purified by dissolving the filter cake in 1000 parts of water at 80 C., filtering, and adding dropwise to the filtrate at 70 C., parts of hydrochloric acid (10%). On cooling, the dyestuif precipitated and was readily separated by filtration. The filter cake was stirred with 200 parts of cold water, refiltered and dried. The dyestuii has the formula:

0 NHZ CH3 I COOH It dyes wool from an acid bath attractive blue shades of good fastness to light and fulling.

Example 4 To a suspensionof 13.2 parts of 5-(l-piperidylsulfonyD-anthranilic acid in 250 parts of water at 75 C. was added 2.25 parts of sodium carbonate as a 5% aqueous solution. To the resulting solution was added a suspension .of 10 parts of sodium acetate and 10.1 parts of l-aminolbromoanthraquinone-Z-sulfonic acid sodium salt in 150 parts of water at 60 C. There was further added 1 part of cuprous chloride and the temperature of the mixture raised to -95" C, and maintained thereat for three hours. To the reaction mixture at 80 C. was added 50 parts of sodium chloride. On cooling to 50 C., the dyestuff precipitated and was then filtered oil.

The dyestufi was purified by dissolving in 600 parts of water, filtering, and to the filtrate at 1 75 C. adding 50 parts of hydrochloric acid 10%) The mixture was cooled and the precipitated dyestufi separated by filtration, the filter cake washed with parts of cold water and redissolved in 100 parts of dilute sodium carbonate solution. 20 parts of sodium chloride was then added to the solution and dilute hydrochloric acid until precipitation had occurred. The precipitate was filtered on? and triturated with a small amount of ammonia and dried. The dyestufi has the formula:

COOH

CHr-CH;

CH2 CHPCi It dyes wool from an acid bath attractive blue shades.

I SOzN Example 5 zgesauoe mixture wa-s-maintainedat 95 C. under stirring for 18 hours. by the addition to the reaction mixture at 80 C. of 110 parts of sodium chloridexand sufficient dilute hydrochloric acid .to cause-precipitation. The filtered product was purified by repeated re-precipitations with dilute hydrochloric acid from solutions containing the dyestufi and sodium chloride. The dyestuff hasrzthe-iformula:

O NHz Example? 6. A mixture of 21.4 parts of. 5= (p-tolylsu1famyl) anthranilic .acid, 20.2 parts of; l aminolebromo anthraquinone- 2 sulfonic acidlsodium salt, 24.2

parts of sodium bicarbonate and"1.5 parts of. cuprous .chloride in 500 partsv of. Water was heatedeto 75-78% C. under stirring for 6 hours. The dyestuff was isolated and purified following essentially the procedure in Example 1. The dyestuff has the formula:

SOaH

COOH

It dyes wool from an acid bath attractive blue shades of good fastness.

Example 7 A mixture of 13.68 parts of 5-diethylsu1famylanthranilic acid, 16.16 parts of l-aminolbromoanthraquinone 2 sulfonic acid sodium salt, 11.58 parts of sodium acetate and 1 part of cuprous chloride in 400 parts of water was stirred at 95 C. for one and one-half hours. The dyestuff was isolated and purified following essentially the procedure in Example 1. The dyestuff has the formula:

(II) NHa SOaH COOH

S OaN The dyestuff wasbroughtndowm It dyes wool, silk and =syntlietie-linean polyamide fibers from an acid bath blue sl'iades' of good light fastness.

Example 8 I SO2NH-GHa-C O OH and yielded attractive reddish-blue shades on wool. The fastness to light was good.

Example 9 To 11.2 parts of 5-[N-methyl-N-(2'-sulfoethyl)sulfamyll-anthranilic acid in 100 parts of water was added 7.4 parts of sodium acetate. Then was added a suspension of 14.2 parts of 1-amino- 1-bromoanthraquinone-Z-sulfonic acid sodium salt in 100 parts of water, and 0.5 part of cuprous chloride. The mixture was stirred at C. until condensation was complete. The dyestuff isolated from the reaction mixture and purified by the usual methods has the formula:

0 NHz SO3H ll 0 NH OOOH I OzNG HaC HaSOaH and dyes wool in blue shades. As various other embodiments of the invention will occur to those skilled in the art, it is not intended that the scope of the patent be limited except as is required by the prior art and the appended claims,

I claim:

8 An aminoanthraquinone pound of the 3. An aminoanthraquinone compound of lthe general formula: general formula: v

NH1 0 N H2 v 15 ozN I wherein :1: represents a radical selected from the group consisting of hydrogen and lower alkyl.

2.An aminoanthraquinone compound of the @0011 general formula. 20 CURT G. VOGT.

O NHa so H REFERENCES CITED The following references are of record in the file of this patent:

' r H UNITED STATES PATENTS O NH Number Name Date 000E 2,195,067 Weinand et a1. Mar. 26, 1940 O FOREIGN PATENTS 0 Number Country Date SMMIQA 554,324 Germany July 11, 1932 COOH l NH v 0 s r c a.

10 4 COOH a: -oooH,. 3 SOIN I f 1 CH3 

